Potassium Bromide → 2-Bromo-6-methyl-4-(trifluoromethyl)aniline

HRID 913807Notes

Reaction equation

HRID 913807 reaction equation
[CH3:1][C:2]1[CH:8]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:6]=[CH:5][C:3]=1[NH2:4].[Br-:13].[K+].B1([O-])OO1.O.O.O.O.[Na+].C(=O)(O)[O-].[Na+]>C(O)(=O)C.N.N.N.N.N.N.O.O.O.O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O>[Br:13][C:5]1[CH:6]=[C:7]([C:9]([F:10])([F:11])[F:12])[CH:8]=[C:2]([CH3:1])[C:3]=1[NH2:4]

Participants

8

Reactant 4

HCID 253877Potassium Bromide4×HCID 516892Sodium BicarbonateHCID 137504374-Amino-3-methylbenzotrifluorideHCID 23693097Sodium;3-oxidodioxaborirane;tetrahydrate4×

Product 1

HCID 534166792-Bromo-6-methyl-4-(trifluoromethyl)aniline

Reagents, catalysts & solvents 3

HCID 16211167Ammonium paramolybdate tetrahydrateCatalyst4×HCID 176Acetic AcidSolventHCID 962WaterSolvent

Procedure

To a suspension of 2-methyl-4-(trifluoromethyl)aniline (7.78 g, 44.4 mmol), potassium bromide (1.59 g, 13.3 mmol), and ammonium heptamolybdate tetrahydrate (140 mg, 0.111 mmol) in acetic acid (40 mL) at room temperature (in a room temperature waterbath) was added sodium perborate tetrahydrate (1.88 g, 12.2 mmol). After 10 min, the reaction was treated with an additional portion of potassium bromide (1.59 g, 13.3 mmol), ammonium heptamolybdate tetrahydrate (140 mg, 0.111 mmol), and sodium perborate tetrahydrate (1.88 g, 12.2 mmol). After 10 min, the reaction was treated with an additional portion of potassium bromide (1.59 g, 13.3 mmol), ammonium heptamolybdate tetrahydrate (140 mg, 0.111 mmol), and sodium perborate tetrahydrate (1.88 g, 12.2 mmol). After 10 min, the reaction was treated with an additional portion of potassium bromide (1.59 g, 13.33 mmol), ammonium heptamolybdate tetrahydrate (140 mg, 0.111 mmol), and sodium perborate tetrahydrate (1.88 g, 12.2 mmol). After 1 h, the reaction was treated with a final portion of everything in half the amounts of the previous additions. After 1 h, the mixture was poured into water, neutralized with solid sodium bicarbonate, extracted into diethyl ether, washed with water, then brine, dried over magnesium sulfate, and concentrated to give 11.3 g (100%) as an oil. 1H-NMR (CDCl3, 500 MHz) δ 7.56 (s, 1H), 7.23 (s, 1H), 4.36 (bs, 2H), 2.23 (s, 3H); 13C-NMR (CDCl3, 126 MHz) δ 145.3, 127.7 (q, J=3.8 Hz), 126.4 (q, J=3.8 Hz), 124.0 (q, J=272 Hz), 120.6 (q, J=34 Hz), 108.2, 18.3. Mass spec.: 253.95 (MH)+.

Workup

  1. waitAfter 10 min
  2. waitAfter 10 min
  3. waitAfter 1 h
  4. additionthe reaction was treated with a final portion of everything in half the amounts of the previous additions
  5. waitAfter 1 h
  6. extractionextracted into diethyl ether
  7. washwashed with water
  8. dry with materialbrine, dried over magnesium sulfate
  9. concentrationconcentrated
  10. customto give 11.3 g (100%) as an oil

Sources & evidence

ORD record
ord-2d55ca11fb7f49f89ff170d3ce86f66e
Source dataset
uspto-grants-2011_09
Patent number
US08026257B2

Reaction notes

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